Nematocidal  heterocyclic amides

ABSTRACT

Disclosed are compounds of Formulae 1, 1a, 1b and 2, 
     
       
         
         
             
             
         
       
     
     wherein
         R 1 , R 1a , R 1b , R 2 , R 3  and R 4  are as defined in the disclosure.
 
Also disclosed are compositions containing the compounds of Formulae 1, 1a and 1b, and methods for controlling a parasitic nematode comprising contacting the parasitic nematode or its environment with a biologically effective amount of a compound or composition of Formulae 1, 1a, 1b and 2.

FIELD OF THE INVENTION

This invention relates to certain heterocyclic amides and theircompositions suitable for agronomic and nonagronomic uses, and methodsof their use for controlling parasitic nematodes in both agronomic andnonagronomic environments.

BACKGROUND OF THE INVENTION

The control of plant-parasitic nematodes is extremely important inachieving high crop efficiency. Nematode-induced root damage can causesignificant reduction in crop yields and quality and thereby result inincreased costs to the consumer. Due to widespread development ofresistance to anthelmintic agents in nematode parasites, nematodescontinue to cause problems in livestock despite the available chemicaltherapeutic agents. The need continues for new compounds which are moreeffective, less costly, less toxic, environmentally safer or havedifferent modes of action.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including allstereoisomers) and compositions containing them and their use forcontrolling a parasitic nematode:

wherein

-   -   R¹ is H or methyl;    -   R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆        alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl or Br;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl;    -   provided that (i) when R¹ and R² are H, then R³ is other than        C₂-C₃ alkenyl, C₂-C₃ alkynyl, cyclopropyl, —CH₂OCH₃, —CH₂SCH₃,        unsubstituted C₂-C₃ alkyl, or C₂-C₃ alkyl substituted with Cl or        Br; (ii) when R¹ is methyl, then R³ is other than ethyl;        and (iii) when R¹ is H and R² is methyl, then R³ is other than        ethyl.

This invention is also directed to compounds of Formula 1a andcompositions containing them and their use for controlling a parasiticnematode:

wherein

-   -   R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆        alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl.

This invention is also directed to compounds of Formula 1a andcompositions containing them and their use for controlling a parasiticnematode:

wherein

-   -   R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆        alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl;    -   provided that (i) when R² is H, then R³ is other than C₂-C₃        alkenyl, C₂-C₃ alkynyl, cyclopropyl, —CH₂OCH₃, —CH₂SCH₃,        unsubstituted C₂-C₃ alkyl, or C₂-C₃ alkyl substituted with Cl or        Br; and (ii) when R² is methyl, then R³ is other than ethyl.

This invention is also directed to compounds of Formula 1b andcompositions containing them and their use for controlling a parasiticnematode:

wherein

-   -   R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆        alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl.

This invention is also directed to compounds of Formula 1b andcompositions containing them and their use for controlling a parasiticnematode:

wherein

-   -   R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆        alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl;    -   provided that (i) when R² is H, then R³ is other than C₂-C₃        alkenyl, C₂-C₃ alkynyl, cyclopropyl, —CH₂OCH₃, —CH₂SCH₃,        unsubstituted C₂-C₃ alkyl, or C₂-C₃ alkyl substituted with Cl or        Br; and (ii) when R² is methyl, then R³ is other than ethyl.

This invention also provides a composition comprising a compound ofFormula 1, 1a or 1b, and at least one additional component selected fromthe group consisting of surfactants, solid diluents and liquid diluents.In one embodiment, this invention also provides a composition forcontrolling a parasitic nematode comprising a compound of Formula 1, 1aor 1b and at least one additional component selected from the groupconsisting of surfactants, solid diluents and liquid diluents, saidcomposition optionally further comprising at least one additionalbiologically active compound or agent.

This invention provides a method for controlling a parasitic nematodecomprising contacting the parasitic nematode or its environment with abiologically effective amount of a compound of Formula 1, 1a or 1b(e.g., as a composition described herein). This invention also relatesto such method wherein the parasitic nematode or its environment iscontacted with a composition comprising a biologically effective amountof a compound of Formula 1, 1a or 1b, and at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents, said composition optionally furthercomprising a biologically effective amount of at least one additionalbiologically active compound or agent.

This invention also provides a method for protecting a seed from aparasitic nematode comprising contacting the seed with a biologicallyeffective amount of a compound of Formula 1, 1a or 1b (e.g., as acomposition described herein). This invention also relates to thetreated seed.

This invention also provides a method for controlling a parasiticnematode comprising contacting the parasitic nematode or its environmentwith a biologically effective amount of a compound of Formula 2

wherein

-   -   Q is a furan, thiophene or thiazole ring substituted with R⁴ at        a carbon atom adjacent to the carbon atom through which the        furan, thiophene or thiazole ring is bonded to the remainder of        Formula 2;    -   R^(1a) is C₁-C₆ alkyl or C₃-C₆ cycloalkyl, each unsubstituted or        substituted with at least one R⁵;    -   R^(1b) is H or C₁-C₃ alkyl; or    -   R^(1a) and R^(1b) are taken together with the carbon atom to        which they are attached to form a 3- to 6-membered cycloalkyl        ring, unsubstituted or substituted with at least one R⁵;    -   R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆        alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano; provided that when R⁴ is Me,        then R³ is other than unsubstituted C₂ alkyl;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl.

This invention also relates to such method wherein the parasiticnematode or its environment is contacted with a composition comprising abiologically effective amount of a compound of Formula 2 and at leastone additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, said compositionoptionally further comprising a biologically effective amount of atleast one additional biologically active compound or agent.

This invention also provides a method for protecting a seed from aparasitic nematode comprising contacting the seed with a biologicallyeffective amount of a compound of Formula 2 (e.g., as a compositiondescribed herein). This invention also relates to the treated seed.

DETAILS OF THE INVENTION

As used herein, the terms “comprises”, “comprising”, “includes”,“including”, “has”, “having”, “contains”, “containing”, “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process or method that comprises alist of elements is not necessarily limited to only those elements butmay include other elements not expressly listed or inherent to suchcomposition, mixture, process or method.

The transitional phrase “consisting of” excludes any element, step oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition or method that includes materials, steps, features,components or elements, in addition to those literally disclosed,provided that these additional materials, steps, features, components orelements do not materially affect the basic and novel characteristic(s)of the claimed invention. The term “consisting essentially of” occupiesa middle ground between “comprising” and “consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising”, it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of”.

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As used to in the present disclosure and claims, the term “nematode”refers to a living organism of the Phylum Nematoda. As generallydefined, a “parasite” lives or grows inside or feeds on another livingorganism (such as a plant, animal or human) described as the “host”. Asreferred to in the present disclosure and claims a “parasitic nematode”is particularly a nematode that injures or damages tissue or causesother forms of disease in plants, animals (particularly vertebrates) orhumans.

A parasite “infestation” refers to the presence of parasites in numbersthat pose a risk to plants, humans or animals. The presence can be inthe environment, e.g., in a human or animal house, or surroundingproperty or structures, on an agricultural crop or other type of plant,in animal bedding, on the skin or fur of an animal, etc. When theinfestation that is referred to is within an animal, e.g., in the bloodor other internal tissues, the term infestation is also intended to besynonymous with the term, “infection,” as that term is generallyunderstood in the art, unless otherwise stated.

As referred to in the present disclosure and claims, the terms“parasiticidal” and “parasiticidally” refers to observable effects on aparasitic nematode to provide protection of a plant, animal or humanfrom the nematode. Parasiticidal effects typically relate to diminishingthe occurrence or activity of the target parasitic nematode. Sucheffects on the nematode include necrosis, death, retarded growth,diminished mobility or lessened ability to remain on or in the hostplant, animal or human, reduced feeding and inhibition of reproduction.These effects on parasitic nematodes provide control (includingprevention, reduction or elimination) of parasitic infestation orinfection of the plant, animal or human. Therefore “control” of aparasitic nematode means achieving a parasiticidal effect on thenematode. The expressions “parasiticidally effective amount” and“biologically effective amount” in the context of applying a chemicalcompound to control a parasitic nematode refer an amount of the compoundthat is sufficient to control the parasitic nematode.

The term “agronomic” refers to the production of field crops such as forfood and fiber and includes the growth of soybeans and other legumes,cereal (e.g., wheat, oats, barley, rye, rice, maize/corn), leafyvegetables (e.g., lettuce, cabbage, and other cole crops), fruitingvegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits),potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stoneand citrus), small fruit (berries, cherries) and other specialty crops(e.g., canola, sunflower, olives).

The term “nonagronomic” refers to other than field crops, such ashorticultural crops (e.g., greenhouse, nursery or ornamental plants notgrown in a field), residential, agricultural, commercial and industrialstructures, turf (e.g., sod farm, pasture, golf course, lawn, sportsfield, etc.), wood products, stored product, agro-forestry andvegetation management, public health (i.e. human) and animal health(e.g., domesticated animals such as pets, livestock and poultry,undomesticated animals such as wildlife) applications.

Nonagronomic applications include protecting an animal from a parasiticnematode by administering a parasiticidally effective (i.e. biologicallyeffective) amount of a compound of the invention, typically in the formof a composition formulated for veterinary use, to the animal to beprotected.

In the above recitations, the term “alkyl”, used either alone or incompound words such as “haloalkyl” includes straight-chain or branchedalkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the differentbutyl, pentyl or hexyl isomers. “Alkenyl” includes straight-chain orbranched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and thedifferent butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includespolyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includesstraight-chain or branched alkynes such as ethynyl, 1-propynyl,2-propynyl and the different butynyl, pentynyl and hexynyl isomers.“Alkynyl” can also include moieties comprised of multiple triple bondssuch as 2,5-hexadiynyl.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl. The term “cycloalkylalkyl” denotes cycloalkylsubstitution on an alkyl moiety. Examples of “cycloalkylalkyl” includecyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moietiesbonded to straight-chain or branched alkyl groups.

The term “halogen”, either alone or in compound words such as“haloalkyl”, or when used in descriptions such as “alkyl substitutedwith halogen” includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, or when used indescriptions such as “alkyl substituted with halogen” said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of “haloalkyl” or “alkyl substituted withhalogen” include F₃C, ClCH₂, CF₃CH₂ and CF₃CCl₂.

The term “alkylthio” includes straight-chain or branched alkylthiomoieties such as methylthio, ethylthio, and the different propylthio,butylthio, pentylthio and hexylthio isomers. “Alkylsulfinyl” includesboth enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl”include CH₃S(═O), CH₃CH₂S(═O), CH₃CH₂CH₂S(═O), (CH₃)₂CHS(═O) and thedifferent butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.Examples of “alkylsulfonyl” include CH₃S(═O)₂, CH₃CH₂S(═O)₂,CH₃CH₂CH₂S(═O)₂, (CH₃)₂CHS(═O)₂, and the different butylsulfonyl,pentylsulfonyl and hexylsulfonyl isomers. The chemical abbreviationsS(O) and S(═O) as used herein represent a sulfinyl moiety. The chemicalabbreviations SO₂, S(O)₂ and S(═O)₂ as used herein represent a sulfonylmoiety.

“Alkylcarbonyl” denotes a straight-chain or branched alkyl moiety bondedto a C(O) moiety. The chemical abbreviations C(O) and C(═O) as usedherein represent a carbonyl moiety. Examples of “alkylcarbonyl” includeC(O)CH₃, C(O)CH₂CH₂CH₃ and C(O)CH(CH₃)₂.

“Alkoxycarbonyl” denotes a straight-chain or branched alkyl moietybonded to a CO₂ moiety. The chemical abbreviations CO₂, C(O)O and C(═O)Oas used herein represent an oxycarbonyl moiety. Examples of“alkoxycarbonyl” include C(O)OCH₃, C(O)OCH₂CH₃, C(O)OCH₂CH₂CH₃ andC(O)OCH(CH₃)₂.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix. For example, C₁-C₆ alkyl designates methyl,ethyl, and the various propyl, butyl, pentyl and hexyl isomers.

As used herein, the following definitions shall apply unless otherwiseindicated. The term “optionally substituted” is used interchangeablywith the phrase “substituted or unsubstituted” or with the term“(un)substituted”. The expression “optionally substituted with 1 to 4substituents” means that no substituent is present (i.e. unsubstituted)or that 1, 2, 3 or 4 substituents are present (limited by the number ofavailable bonding positions). Unless otherwise indicated, an optionallysubstituted group may have a substituent at each substitutable positionof the group, and each substitution is independent of the other.

A wide variety of synthetic methods are known in the art to enablepreparation of aromatic and nonaromatic heterocyclic rings and ringsystems; for extensive reviews see the eight volume set of ComprehensiveHeterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief,Pergamon Press, Oxford, 1984 and the twelve volume set of ComprehensiveHeterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V.Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds selected from Formula 1, 1a or 1b, may exist in more than oneform, and Formula 1, 1a or 1b thus includes all crystalline andnon-crystalline forms of the compounds that Formula 1, 1a or 1brepresents. Non-crystalline forms include embodiments which are solidssuch as waxes and gums as well as embodiments which are liquids such assolutions and melts. Crystalline forms include embodiments whichrepresent essentially a single crystal type and embodiments whichrepresent a mixture of polymorphs (i.e. different crystalline types).The term “polymorph” refers to a particular crystalline form of achemical compound that can crystallize in different crystalline forms,these forms having different arrangements and/or conformations of themolecules in the crystal lattice. Although polymorphs can have the samechemical composition, they can also differ in composition due thepresence or absence of co-crystallized water or other molecules, whichcan be weakly or strongly bound in the lattice. Polymorphs can differ insuch chemical, physical and biological properties as crystal shape,density, hardness, color, chemical stability, melting point,hygroscopicity, suspensibility, dissolution rate and biologicalavailability. One skilled in the art will appreciate that a polymorph ofa compound represented by Formula 1, 1a or 1b can exhibit beneficialeffects (e.g., suitability for preparation of useful formulations,improved biological performance) relative to another polymorph or amixture of polymorphs of the same compound represented by Formula 1, 1aor 1b. Preparation and isolation of a particular polymorph of a compoundrepresented by Formula 1, 1a or 1b can be achieved by methods known tothose skilled in the art including, for example, crystallization usingselected solvents and temperatures.

Embodiments of the present invention as described in the Summary of theInvention include those described below. In the following Embodiments,reference to a compound of Formula 1, 1a or 1b includes the definitionsof substituents specified in the Summary of the Invention unless furtherdefined in the Embodiments.

-   -   Embodiment 1. A compound of Formula 1a.    -   Embodiment 2. A compound of Formula 1b.    -   Embodiment 3. A compound of Formula 1, 1a or 1b wherein R² is H.    -   Embodiment 4. A compound of Formula 1, 1a or 1b wherein R³ is        C₂-C₆ alkyl or C₃-C₆ cycloalkyl, each unsubstituted or        substituted with at least one R⁶.    -   Embodiment 4a. A compound of Formula 1, 1a or 1b wherein R³ is        C₂-C₆ alkyl or C₃-C₆ cycloalkyl.    -   Embodiment 4b. A compound of Formula 1, 1a or 1b wherein R³ is        C₃-C₆ alkyl or cyclopropyl.    -   Embodiment 4c. A compound of Formula 1, 1a or 1b wherein R³ is        isopropyl, s-butyl, t-butyl, CH₂C(CH₃)₃ or cyclopropyl.    -   Embodiment 4d. A compound of Formula 1, 1a or 1b wherein R³ is        t-butyl or cyclopropyl.    -   Embodiment 4e. A compound of Formula 1, 1a or 1b wherein R³ is        isopropyl.    -   Embodiment 4f. A compound of Formula 1, 1a or 1b wherein R³ is        s-butyl.    -   Embodiment 4g. A compound of Formula 1, 1a or 1b wherein R³ is        t-butyl.    -   Embodiment 4h. A compound of Formula 1, 1a or 1b wherein R³ is        CH₂C(CH₃)₃.    -   Embodiment 4i. A compound of Formula 1, 1a or 1b wherein R³ is        cyclopropyl.    -   Embodiment 5. A compound of Formula 1 wherein R³ is isopropyl.    -   Embodiment 5a. A compound of Formula 1 wherein R³ is s-butyl.    -   Embodiment 5b. A compound of Formula 1 wherein R³ is t-butyl.    -   Embodiment 5c. A compound of Formula 1 wherein R³ is CH₂C(CH₃)₃.    -   Embodiment 5d. A compound of Formula 1 wherein R³ is        cyclopropyl.    -   Embodiment 6. A compound of Formula 1a wherein R³ is isopropyl.    -   Embodiment 6a. A compound of Formula 1a wherein R³ is s-butyl.    -   Embodiment 6b. A compound of Formula 1a wherein R³ is t-butyl.    -   Embodiment 6c. A compound of Formula 1a wherein R³ is        CH₂C(CH₃)₃.    -   Embodiment 6d. A compound of Formula 1a wherein R³ is        cyclopropyl.    -   Embodiment 7. A compound of Formula 1b wherein R³ is isopropyl.    -   Embodiment 7a. A compound of Formula 1b wherein R³ is s-butyl.    -   Embodiment 7b. A compound of Formula 1b wherein R³ is t-butyl.    -   Embodiment 7c. A compound of Formula 1b wherein R³ is        CH₂C(CH₃)₃.    -   Embodiment 7d. A compound of Formula 1b wherein R³ is        cyclopropyl.    -   Embodiment 8. A compound of Formula 1, 1a or 1b wherein R⁴ is Cl        or Br.    -   Embodiment 8a. A compound of Formula 1, 1a or 1b wherein R⁴ is        Cl.    -   Embodiment 8b. A compound of Formula 1, 1a or 1b wherein R⁴ is        Br.    -   Embodiment 9. A compound of Formula 1 wherein R⁴ is Cl or Br.    -   Embodiment 9a. A compound of Formula 1 wherein R⁴ is Cl.    -   Embodiment 9b. A compound of Formula 1 wherein R⁴ is Br.    -   Embodiment 10. A compound of Formula 1a wherein R⁴ is Cl or Br.    -   Embodiment 10a. A compound of Formula 1a wherein R⁴ is Cl.    -   Embodiment 10b. A compound of Formula 1a wherein R⁴ is Br.    -   Embodiment 11. A compound of Formula 1b wherein R⁴ is Cl or Br.    -   Embodiment 11a. A compound of Formula 1b wherein R⁴ is Cl.    -   Embodiment 11b. A compound of Formula 1b wherein R⁴ is Br.

Embodiments of this invention, including Embodiments 1-11b above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1, 1a or 1b but also to the startingcompounds and intermediate compounds useful for preparing the compoundsof Formula 1, 1a or 1b. In addition, embodiments of this invention,including Embodiments 1-11b above as well as any other embodimentsdescribed herein, and any combination thereof, pertain to thecompositions and methods of the present invention.

Combinations of Embodiments 1-11b are illustrated by:

Embodiment A

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is C₂-C₆ alkyl or C₃-C₆ cycloalkyl, each unsubstituted or        substituted with at least one R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl.

Embodiment B

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is C₂-C₆ alkyl or C₃-C₆ cycloalkyl; and    -   R⁴ is Cl or Br.

Embodiment C

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is C₃-C₆ alkyl or cyclopropyl; and    -   R⁴ is Cl or Br.

Embodiment D

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is t-butyl or cyclopropyl; and    -   R⁴ is Cl or Br.

Embodiment E

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is isopropyl, s-butyl, t-butyl, CH₂C(CH₃)₃ or cyclopropyl;        and    -   R⁴ is Cl or Br.

Embodiment E1

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is isopropyl, s-butyl, t-butyl, CH₂C(CH₃)₃ or cyclopropyl;        and    -   R⁴ is Cl.

Embodiment E2

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is isopropyl, s-butyl, t-butyl, CH₂C(CH₃)₃ or cyclopropyl;        and    -   R⁴ is Br.

Embodiment F1

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is isopropyl; and    -   R⁴ is Cl.

Embodiment F2

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is s-butyl; and    -   R⁴ is Cl.

Embodiment F3

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is t-butyl; and    -   R⁴ is Cl.

Embodiment F4

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is CH₂C(CH₃)₃; and    -   R⁴ is Cl.

Embodiment F5

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is cyclopropyl; and    -   R⁴ is Cl.

Embodiment G1

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is isopropyl; and    -   R⁴ is Br.

Embodiment G2

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is s-butyl; and    -   R⁴ is Br.

Embodiment G3

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is t-butyl; and    -   R⁴ is Br.

Embodiment G4

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is CH₂C(CH₃)₃; and    -   R⁴ is Br.

Embodiment G5

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is cyclopropyl; and    -   R⁴ is Br.

Embodiment H

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is C₂-C₆ alkyl or C₃-C₆ cycloalkyl, each unsubstituted or        substituted with at least one R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl.

Embodiment I

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is C₂-C₆ alkyl or C₃-C₆ cycloalkyl; and    -   R⁴ is Cl or Br.

Embodiment J

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is C₃-C₆ alkyl or cyclopropyl; and    -   R⁴ is Cl or Br.

Embodiment K

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is t-butyl or cyclopropyl; and    -   R⁴ is Cl or Br.

Embodiment L

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is isopropyl, s-butyl, t-butyl, CH₂C(CH₃)₃ or cyclopropyl;        and    -   R⁴ is Cl or Br.

Embodiment M1

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is isopropyl, s-butyl, t-butyl, CH₂C(CH₃)₃ or cyclopropyl;        and    -   R⁴ is Cl.

Embodiment M2

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is isopropyl, s-butyl, t-butyl, CH₂C(CH₃)₃ or cyclopropyl;        and    -   R⁴ is Br.

Embodiment N1

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is isopropyl; and    -   R⁴ is Cl.

Embodiment N2

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is s-butyl; and    -   R⁴ is Cl.

Embodiment N3

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is t-butyl; and    -   R⁴ is Cl.

Embodiment N4

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is CH₂C(CH₃)₃; and    -   R⁴ is Cl.

Embodiment N5

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is cyclopropyl; and    -   R⁴ is Cl.

Embodiment O1

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is isopropyl; and    -   R⁴ is Br.

Embodiment O2

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is s-butyl; and    -   R⁴ is Br.

Embodiment O3

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is t-butyl; and    -   R⁴ is Br.

Embodiment O4

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is CH₂C(CH₃)₃; and    -   R⁴ is Br.

Embodiment O5

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is cyclopropyl; and    -   R⁴ is Br.

Embodiment P1

A compound of Formula 1 wherein

-   -   R² is H;    -   R³ is —CR^(6a)R^(6b)R^(6c);    -   R⁴ is Cl or Br;    -   R^(6a) is H, C₁-C₃ alkyl, C₂-C₃ alkenyl or C₃-C₆ cycloalkyl;    -   R^(6b) is C₁-C₃ alkyl;    -   R^(6c) is H, halogen, cyano, C₁-C₃ alkoxy, C₁-C₃ alkylthio,        C₁-C₃ alkylsulfinyl, C₁-C₃ alkylsulfonyl or        —CR^(7a)R^(7b)R^(7c);    -   R^(7a) is H, halogen, cyano, C₁-C₃ alkoxy, C₁-C₃ alkylthio,        C₁-C₃ alkylsulfinyl, C₁-C₃ alkylsulfonyl or C₁-C₂ alkyl;    -   R^(7b) is H, halogen, cyano or C₁-C₂ alkyl; and    -   R^(7c) is H, halogen, cyano or C₁-C₂ alkyl.

Embodiment P2

A compound of Formula 1a wherein

-   -   R² is H;    -   R³ is —CR^(6a)R^(6b)R^(6c);    -   R⁴ is Cl or Br;    -   R^(6a) is H, C₁-C₃ alkyl, C₂-C₃ alkenyl or C₃-C₆ cycloalkyl;    -   R^(6b) is C₁-C₃ alkyl;    -   R^(6c) is H, halogen, cyano, C₁-C₃ alkoxy, C₁-C₃ alkylthio,        C₁-C₃ alkylsulfinyl, C₁-C₃ alkylsulfonyl or        —CR^(7a)R^(7b)R^(7c);    -   R^(7a) is H, halogen, cyano, C₁-C₃ alkoxy, C₁-C₃ alkylthio,        C₁-C₃ alkylsulfinyl, C₁-C₃ alkylsulfonyl or C₁-C₂ alkyl;    -   R^(7b) is H, halogen, cyano or C₁-C₂ alkyl; and    -   R^(7c) is H, halogen, cyano or C₁-C₂ alkyl.

Embodiment P3

A compound of Formula 1b wherein

-   -   R² is H;    -   R³ is —CR^(6a)R^(6b)R^(6c);    -   R⁴ is Cl or Br;    -   R^(6a) is H, C₁-C₃ alkyl, C₂-C₃ alkenyl or C₃-C₆ cycloalkyl;    -   R^(6b) is C₁-C₃ alkyl;    -   R^(6c) is H, halogen, cyano, C₁-C₃ alkoxy, C₁-C₃ alkylthio,        C₁-C₃ alkylsulfinyl, C₁-C₃ alkylsulfonyl or        —CR^(7a)R^(7b)R^(7c);    -   R^(7a) is H, halogen, cyano, C₁-C₃ alkoxy, C₁-C₃ alkylthio,        C₁-C₃ alkylsulfinyl, C₁-C₃ alkylsulfonyl or C₁-C₂ alkyl;    -   R^(7b) is H, halogen, cyano or C₁-C₂ alkyl; and    -   R^(7c) is H, halogen, cyano or C₁-C₂ alkyl.

Embodiment Q1

A composition comprising (i) a compound of Formula 1a and a compound ofFormula 1b, wherein the ratio of 1b to 1a is at least 55:45; and

-   -   wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl; and    -   (ii) at least one additional component selected from the group        consisting of surfactants, solid diluents and liquid diluents.

Embodiment Q2

A composition comprising (i) a compound of Formula 1a and a compound ofFormula 1b, wherein the ratio of 1b to 1a is at least 65:35; and

-   -   wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl; and    -   (ii) at least one additional component selected from the group        consisting of surfactants, solid diluents and liquid diluents.

Embodiment Q3

A composition comprising (i) a compound of Formula 1a and a compound ofFormula 1b, wherein the ratio of 1b to 1a is at least 75:25; and

-   -   wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl; and    -   (ii) at least one additional component selected from the group        consisting of surfactants, solid diluents and liquid diluents.

Embodiment Q4

A composition comprising (i) a compound of Formula 1a and a compound ofFormula 1b, wherein the ratio of 1b to 1a is at least 85:15; and

-   -   wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl; and    -   (ii) at least one additional component selected from the group        consisting of surfactants, solid diluents and liquid diluents.

Embodiment Q5

A composition comprising (i) a compound of Formula 1a and a compound ofFormula 1b, wherein the ratio of 1b to 1a is at least 95:5; and

-   -   wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl; and    -   (ii) at least one additional component selected from the group        consisting of surfactants, solid diluents and liquid diluents.

Embodiment Q6

A composition comprising (i) a compound of Formula 1a and a compound ofFormula 1b, wherein the ratio of 1b to 1a is at least 97:3; and

-   -   wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl; and    -   (ii) at least one additional component selected from the group        consisting of surfactants, solid diluents and liquid diluents.

Embodiment Q7

A composition comprising (i) a compound of Formula 1a and a compound ofFormula 1b, wherein the ratio of 1b to 1a is at least 99:1; and

-   -   wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl; and    -   (ii) at least one additional component selected from the group        consisting of surfactants, solid diluents and liquid diluents.

Embodiment Q8

A composition comprising (i) a compound of Formula 1a and a compound ofFormula 1b, wherein the ratio of 1b to 1a is essentially 100:0; and

-   -   wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,        C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl; and    -   (ii) at least one additional component selected from the group        consisting of surfactants, solid diluents and liquid diluents.

Embodiment R1

A method for controlling a soil-dwelling nematode comprising contactingthe nematode or its environment with a biologically effective amount ofa compound selected from Formula 2,

wherein

-   -   Q is a furan, thiophene or thiazole ring substituted with R⁴ at        a carbon atom adjacent to the carbon atom through which the        furan, thiophene or thiazole ring is bonded to the remainder of        Formula 2;    -   R^(1a) is C₁-C₆ alkyl or C₃-C₆ cycloalkyl, each unsubstituted or        substituted with at least one R⁵;    -   R^(1b) is H or C₁-C₃ alkyl; or    -   R^(1a) and R^(1b) are taken together with the carbon atom to        which they are attached to form a 3- to 6-membered cycloalkyl        ring, unsubstituted or substituted with at least one R⁵;    -   R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆        cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆        alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted or        substituted with at least one R⁵;    -   R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆        cycloalkyl, each unsubstituted or substituted with at least one        R⁶;    -   R⁴ is Cl, Br, I, CH₃, CF₃ or cyano; provided that when R⁴ is Me,        then R³ is other than unsubstituted C₂ alkyl;    -   each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, or C₁-C₃        alkylsulfonyl;    -   each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆        cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃        alkylsulfonyl or SiR^(a)R^(b)R^(c); and    -   each R^(a), R^(b) and R^(c) is independently C₁-C₆ alkyl.

Embodiment R2

The method of Embodiment R1 wherein Q is selected from the groupconsisting of:

Embodiment R3

The method of Embodiment R1 wherein Q is Q-1.

Specific embodiments include compounds of Formula 1 and 1b selected fromthe group consisting of (compound numbers refer to Index Tables A-C2):

compound 9;compound 11;compound 26;compound 40;compound 43;compound 78;compound 80; andcompound 84.

Specific embodiments further include compounds of Formula 1b selectedfrom the group consisting of (compound numbers refer to Index TablesA-C2):

compound 9;compound 11;compound 26;compound 40;compound 43;compound 78;compound 80; andcompound 84.

Of note is that compounds of this invention are characterized byfavorable metabolic and/or soil residual patterns and exhibit activitycontrolling a spectrum of agronomic and nonagronomic parasiticnematodes.

Of particular note, for reasons of parasitic nematode control spectrumand economic importance, protection of agronomic crops from damage orinjury caused by parasitic nematodes by controlling parasitic nematodesare embodiments of the invention. Compounds of this invention because oftheir favorable translocation properties or systemicity in plants alsoprotect foliar or other plant parts which are not directly contactedwith a compound of Formula 1, 1a or 1b or a composition comprising thecompound.

Also noteworthy as embodiments of the present invention are compositionscomprising a compound of any of the preceding Embodiments, as well asany other embodiments described herein, and any combinations thereof,and at least one additional component selected from the group consistingof a surfactant, a solid diluent and a liquid diluent, said compositionsoptionally further comprising at least one additional biologicallyactive compound or agent.

Further noteworthy as embodiments of the present invention arecompositions for controlling a parasitic nematode comprising a compoundof any of the preceding Embodiments, as well as any other embodimentsdescribed herein, and any combinations thereof, and at least oneadditional component selected from the group consisting of a surfactant,a solid diluent and a liquid diluent, said compositions optionallyfurther comprising at least one additional biologically active compoundor agent. Embodiments of the invention further include methods forcontrolling a parasitic nematode comprising contacting the parasiticnematode or its environment with a biologically effective amount of acompound of any of the preceding Embodiments (e.g., as a compositiondescribed herein).

Embodiments of the invention also include a composition comprising acompound of any of the preceding Embodiments, in the form of a soildrench liquid formulation. Embodiments of the invention further includemethods for controlling a parasitic nematode comprising contacting thesoil with a liquid composition as a soil drench comprising abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include a spray composition forcontrolling a parasitic nematode comprising a biologically effectiveamount of a compound of any of the preceding Embodiments and apropellant. Embodiments of the invention further include a baitcomposition for controlling a parasitic nematode comprising abiologically effective amount of a compound of any of the precedingEmbodiments, one or more food materials, optionally an attractant, andoptionally a humectant.

Embodiments of the invention also include methods for protecting a seedfrom a parasitic nematode comprising contacting the seed with abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include methods for controlling aparasitic nematode comprising contacting the parasitic nematode or itsenvironment with a biologically effective amount of a compound ofFormula 1, 1a, 1b or 2 (e.g., as a composition described herein),provided that the methods are not methods of medical treatment of ahuman or animal body by therapy.

This invention also relates to such methods wherein the parasiticnematode or its environment is contacted with a composition comprising abiologically effective amount of a compound of Formula 1, 1a, 1b or 2,and at least one additional component selected from the group consistingof surfactants, solid diluents and liquid diluents, said compositionoptionally further comprising a biologically effective amount of atleast one additional biologically active compound or agent, providedthat the methods are not methods of medical treatment of a human oranimal body by therapy.

One or more of the following methods and variations as described inSchemes 1-3 can be used to prepare the compounds of Formulae 1, 1a, 1band 2. The definitions of Q, R^(1a), R^(1b), R², R³ and R⁴ in thecompounds of Formulae 2-8b below are as defined above in the Summary ofthe Invention unless otherwise noted. Room temperature is between about20 and 25° C.

Compounds of Formula 2 can be prepared by the reaction of compounds ofFormula 3, wherein LG is a leaving group such as halogen, with amines ofFormula 4 as shown in Scheme 1. When LG is halogen, the reaction istypically conducted in the presence of a base and in a suitable solvent.Suitable bases include amines such as triethylamine, pyridine andpicoline, inorganic metal salts such as carbonates, bicarbonates,hydroxides and alkoxides, including sodium and potassium carbonate,sodium and potassium bicarbonate, sodium hydroxide and sodium ethoxide.The choice of a suitable solvent is dependent on the nature of LG, thebase, and reaction conditions selected. Typical solvents includealiphatic hydrocarbons such as hexane, cyclohexane and heptane, aromatichydrocarbons such as toluene and xylene, halogenated hydrocarbons suchas dichloromethane, dichloroethane and chlorobenzene, ethers such asdiethyl ether, tetrahydrofuran, dioxane and dimethoxyethane, esters suchas ethyl acetate, amides such as DMF, DMAC and N-methylpyrrolidone,nitriles such as acetonitrile, ketones such as acetone and MEK, andpolar protic solvents such as ethanol and water.

Compounds of Formula 2 can also be prepared by the reaction of compoundsof Formula 5 with amines of Formula 4 as shown in Scheme 2. In thismethod, an amide coupling reagent such as HATU(1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxid hexafluorophosphate), EDC(1-ethyl-3-(3-dimethylaminopropyl)carbodiimide) is used. Reactionconditions for these amide couplings are known in the art.

Compounds of Formula 1 are a subset of the compounds of Formula 2, andcan be prepared in the manner described above for the preparation ofcompounds of Formula 2.

The enantiomeric structures of Formulae 1a and 1b can be prepared asshown in Scheme 3 by methods and conditions similar to those describedin Schemes 1 and 2. For example, as shown in Scheme 3, coupling of furanof Formula 6 with either chiral amine of Formula 7a or 7b yieldscompounds of Formula 8a or 8b, respectively. Amines of Formulae 7a and7b are commercially available or can be prepared by chiral resolution ofthe corresponding racemic amines by known methods.

Alternatively, compounds of Formula 1 can be prepared as racemicmixtures, and the compounds of Formulae 1a and 1b can be separated intotheir respective enantiomers by chiral column chromatography. A largevariety of chiral columns exist for separations of this type.

Compounds of Formulae 1, 1a, 1b and 2 wherein R² is other than H canalso be prepared from their respective analogs wherein R² is H byreaction with the appropriately substituted alkyl, acyl or otherreagent.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1, 1a, 1b or 2 may not becompatible with certain functionalities present in the intermediates. Inthese instances, the incorporation of protection/deprotection sequencesor functional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula 1. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula 1, 1a, 1b or 2.

One skilled in the art will also recognize that compounds of Formula 1,1a, 1b or 2 and the intermediates described herein can be subjected tovarious electrophilic, nucleophilic, radical, organometallic, oxidation,and reduction reactions to add substituents or modify existingsubstituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Synthesis Examples are, therefore, to beconstrued as merely illustrative, and not limiting of the disclosure inany way whatsoever. Steps in the following Synthesis Examples illustratea procedure for each step in an overall synthetic transformation, andthe starting material for each step may not have necessarily beenprepared by a particular preparative run whose procedure is described inother Examples or Steps. ¹H NMR spectra are reported in ppm downfieldfrom tetramethylsilane; “s” means singlet, “d” means doublet, “dd” meansdoublet of doublets, “br s” means broad singlet. Room temperature isbetween about 20 and 25° C. “DMF” is N,N-dimethylformamide.

Synthesis Example 1 Preparation of2-chloro-N-[(1S)-1-cyclopropylethyl]-3-furancarboxamide and2-chloro-N-[(1R)-1-cyclopropylethyl]-3-furancarboxamide (compounds 11,44 and 45) Step A: Preparation of 2-chloro-3-furancarboxylic acid

To a solution of diisopropylamine (10.3 g, 102 mmol) in THF (20 mL) wasadded 2.5M n-BuLi (6.5 g, 102 mmol) in hexane at −78° C. and thereaction mixture was slowly warmed to −40° C. 3-Furancarboxylic acid (5g, 41 mmol) in THF (20 mL was then added and the reaction mixture wasstirred for 30 minutes. Hexachloroethane (10.60 g, 45.68 mmol) in THF(20 mL) was slowly added at −78° C. and the reaction mixture was stirredfor 16 hours. TLC analysis (5% MeOH in DCM) showed completion of thereaction. The reaction mixture was cooled to 0° C., quenched with 1NHCl, and extracted with ethyl acetate (3×). The combined organic layerswere washed with brine and dried over Na₂SO₄. The solvent was evaporatedunder reduced pressure and the obtained crude product was purified bysolvent washing to give 2.8 g of the title product as a brown solid. ¹HNMR (CDCl₃, 400 MHz): δ 10.2 (br s, 1H), 7.33 (d, 1H), 6.81 (d, 1H).Mass spec: (M-1)=145.

Step B: Preparation of2-chloro-N-[(1S)-1-cyclopropylethyl]-3-furancarboxamide and2-chloro-N-[(1R)-1-cyclopropylethyl]-3-furancarboxamide

To a solution of 2-chloro-3-furancarboxylic acid (1 g, 6.84 mmol) in DCM(25 mL) was added α-methylcyclopropanemethanamine hydrochloride (1:1)(0.75 g, 6.16 mmol), EDC-HCl (2 g, 10.27 mmol), DMAP (0.83 g 6.84 mmol),and the reaction mixture was stirred at room temperature for 6 hours,after which time TLC analysis (50% ethyl acetate in petroleum ether)showed completion of the reaction. The reaction mixture was quenchedwith water and extracted with ethyl acetate (3×). The combined organiclayers were washed with water, brine, and then dried over Na₂SO₄. Thesolvent was evaporated under reduced pressure, and the crude product waspurified on a silica gel column eluted with 20% ethyl acetate/petroleumether to provide 0.7 g of the title compound as a white solid. ¹H NMR(CDCl₃, 400 MHz): δ 7.31 (d, 1H), 6.82 (d, 1H), 6.19 (br s, 1H), 3.6 (m,1H), 1.57 (d, 3H), 0.93 (m, 1H), 0.53 (m, 2H), 0.49 (m, 1H), 0.27 (m,1H). Mass spec: (M+1)=214.

The 1S and 1R isomers were separated by chiral preparative HPLC,yielding two stereoisomers with optical rotations [α] of −21.5 and +21.2(c 0.5, chloroform).

Synthesis Example 2 Preparation of2-chloro-N-(1,2,2-trimethylpropyl)-3-furancarboxamide (compound 27) StepA: Preparation of 2-chloro-3-furancarbonyl chloride

Under a nitrogen atmosphere, 2-chloro-3-furancarboxylic acid (1.0 g, 6.8mmol) was suspended in 100 mL of anhydrous dichloromethane.Oxalylchloride (0.98 mL, 11.4 mmol) was then added followed by 1 drop ofDMF. The reaction mixture was stirred overnight, and the solvent wassubsequently removed under reduced pressure to yield 852 mg (76%) of atan oil. ¹H NMR (CDCl₃, 500 MHz): δ 7.37 (d, J=2.4 Hz, 1H), 6.89 ppm (d,J=2.2 Hz, 1H).

A stock solution was prepared [75 mg/5 mL] in dichloromethane to be usedin further reactions.

Step B: Preparation of2-chloro-N-(1,2,2-trimethylpropyl)-3-furancarboxamide

To a solution of 2-chloro-3-furancarbonyl chloride (100 mg, 0.61 mmol)in 6.6 mL of anhydrous dichloromethane was added3-amino-2,2-dimethylbutane (90 μL, 0.67 mmol) under a nitrogenatmosphere. Triethylamine (136 μL, 0.98 mmol) was then added and themixture stirred at room temperature overnight. The solution was thenwashed with water, concentrated in the presence of Celite®, and purifiedby chromatography (0-20% EtOAc:hexanes) to yield 64 mg (46%) of thetitle compound as a tan oil. ¹H NMR (CDCl₃, 500 MHz): δ 7.32 (d, J=2.2Hz, 1H), 6.85 (d, J=2.2 Hz, 1H), 6.12-6.20 (m, 1H), 4.05 (dq, J=9.5, 6.8Hz, 1H), 1.15 (d, J=6.8 Hz, 3H), 0.84-1.06 ppm (s, 9H). LC/MS m/z[M+H]⁺: 230.3.

Synthesis Example 2A Preparation of2-chloro-N-[(1S)-1,2,2-trimethylpropyl]-3-furancarboxamide (compound 40)Step A: Preparation of2-chloro-N-[(1S)-1,2,2-trimethylpropyl]-3-furancarboxamide

To a solution of 2-chloro-3-furancarbonyl chloride (75 mg, 0.46 mmol) in5 mL of anhydrous dichloromethane was added(S)-(+)-3-amino-2,2-dimethylbutane (67 μL, 0.50 mmol) under a nitrogenatmosphere. Triethylamine (188 μL, 1.35 mmol) was then added and themixture stirred at room temperature overnight. The solution was thenwashed with water, concentrated in the presence of Celite®, and purifiedby chromatography (0-20% EtOAc:hexanes) to yield 33 mg (31%) of thetitle compound as a white solid. ¹H NMR (CDCl₃, 500 MHz): δ 7.32 (d,J=2.2 Hz, 1H), 6.85 (d, J=2.2 Hz, 1H), 6.12-6.20 (m, 1H), 4.05 (dq,J=9.5, 6.8 Hz, 1H), 1.15 (d, J=6.8 Hz, 3H), 0.84-1.06 ppm (s, 9H). LC/MSm/z [M+H]⁺: 230.4. [α]+10.7° (c 3.65, methanol).

Synthesis Example 2b Preparation of2-chloro-N-[(1R)-1,2,2-trimethylpropyl]-3-furancarboxamide (compound 41)Step A: Preparation of2-chloro-N-[(1R)-1,2,2-trimethylpropyl]-3-furancarboxamide

To a solution of 2-chloro-3-furancarbonyl chloride (75 mg, 0.46 mmol) in5 mL of anhydrous dichloromethane was added(R)-(+)-3-amino-2,2-dimethylbutane (67 μL, 0.50 mmol) under a nitrogenatmosphere. Triethylamine (188 μL, 1.35 mmol) was then added and themixture stirred at room temperature overnight. The solution was thenwashed with water, concentrated in the presence of Celite®, and purifiedby chromatography (0-20% EtOAc:hexanes) to yield 38 mg (36%) of thetitle compound as a white solid. ¹H NMR (CDCl₃, 500 MHz): δ 7.32 (d,J=2.2 Hz, 1H), 6.85 (d, J=2.2 Hz, 1H), 6.12-6.20 (m, 1H), 4.05 (dq,J=9.5, 6.8 Hz, 1H), 1.15 (d, J=6.8 Hz, 3H), 0.84-1.06 ppm (s, 9H). LC/MSm/z [M+H]⁺: 230.3. [α] −9.09° (c 3.85, methanol).

Specific compounds of Formula 1, 1a, 1b or 2, prepared by the methodsand variations as described in preceding Schemes 1-3 and SynthesisExample 1, 2, 2a and 2b, are shown in the Index Tables below. Thefollowing abbreviations may be used: Cmpd means Compound, t is tertiary,Me is methyl, and Et is ethyl. A “-” in a structure fragment denotes theattachment point of the fragment to the remainder of the molecule. Theabbreviation “Ex.” stands for “Example” and is followed by a numberindicating in which Synthesis Example the compound is prepared.

Columns titled “MS” contain mass spectral data. Columns titled “MP”contain melting point range data. In instances where a single column istitled “MS/MP”, an entry in this column consisting of a range (e.g.,120-122) represents a melting point range, while an entry in this columnconsisting of a single number (e.g., 208.1) represents mass spectraldata. For mass spectral data, the numerical value reported is themolecular weight of the observed molecular ion formed by addition of H⁺(molecular weight of 1) to the molecule having the greatest isotopicabundance (i.e. M). The reported mass spectral peaks were observed bymass spectrometry using atmospheric pressure chemical ionization (AP⁺).

INDEX TABLE A

R⁴ is Me Compd. No. R¹ R² R³ MS MP 1 H H —CH(Me)Et 75-78 2 H Mecyclopropyl 208.1 3 H H methyl 80-83 4 H H isopropyl 68-71 5 H Hpropyl * * 6 H H cyclopropyl 64-68 7 Me H cyclopropyl 78-82 80  H H—CH₂C(Me)₃ 104-108 R⁴ is Cl Compd. No. R¹ R² R³ MS MP  8 Me Hcyclopropyl 62-63  9 H H —CH₂CH₂(cyclopropyl) 242.1 10 Me H isopropyl230.3 11 (Ex. 1) H H cyclopropyl 82-86 12 Me H —CH₂OMe * * 13 H H—CH₂OMe 55-56 14 Me H —CH₂SMe 59-60 15 Me H —CH₂SO₂Me 100-101 16 H Hethyl 85-86 17 H H propyl * * 18 Me H —CH₂C(Me)₃ * * 19 H H —CH₂CH(Me)₂230.3 20 H H cyclopentyl 242.4 21 H H cyclohexyl 256.4 22 H H1-methylcyclopropyl 228.3 23 H H cyclobutyl 228.3 24 H H —CF₃ 242.3 25Me H —CH₂S(O)Me 134-135 26 H H isopropyl 81-84 27 (Ex. 2) H H t-butyl230.4 28 H H —CH₂SMe 234.3 29 H H pentyl 244.4 30 H H 4-methylpentyl258.4 31 H Me cyclopropyl 229.2 78 H H —CH₂C(Me)₃ 244.3 R⁴ is Br Compd.No. R¹ R² R³ MS MP 32 H H cyclopropyl 54-57 33 H H isopropyl 58-59 34 HH propyl * * 35 H H t-butyl * * R⁴ is CN Compd. No. R¹ R² R³ MS 79 H H—C(Me)₂Et 235.2 97 H H —CH₂C(Me)₃ * 98 H H —CH₂CH(Me)₂ * R⁴ is I Compd.No. R¹ R² R³ MS MP 83 H H —CH₂C(Me)₃ 68-72 88 H H t-butyl 322.4 * SeeIndex Table D for ¹H NMR data.

INDEX TABLE B-1

R⁴ is Me Cmpd. No. R³ MP Optical Rotation 36 cyclopropyl 70-73 39t-butyl 63-64 84 —CH₂C(Me)₃ 130-134 −30.35 (c 0.1, chloroform) 96isopropyl 51-55 R⁴ is Cl Cmpd. No. R³ MS MP Optical Rotation 41 (Ex. 2b)t-butyl 230.3 −9.09 (c 3.85, methanol)  45 (Ex. 1)  cyclopropyl 144-148−21.5 (c 0.1, chloroform) 75 isopropyl 216.1 −20.0 (c 0.1, chloroform)76 ethyl 64-65 R⁴ is Br Cmpd. No. R³ MP Optical Rotation 38 t-butyl89-90 74 cyclopropyl 70-73 R⁴ is I Cmpd. No. R³ MS MP Optical Rotation 86 t-butyl 322.1 −12.66 (c 0.4, chloroform) 102 —CH₂C(Me)₃ 94-98 −22.8(c 0.25, chloroform)

INDEX TABLE B-2

R⁴ is Me Cmpd. No. R³ MS MP Optical Rotation 37 cyclopropyl 70-73 85—CH₂C(Me)₃ 132-136 +23.62 (c 0.25, chloroform) 94 t-butyl 213.4 101 isopropyl 53-54 R⁴ is Cl Cmpd. No. R³ MS MP Optical Rotation 40 (Ex. 2a)t-butyl 230.4 +10.7 (c 3.65, methanol)  43 isopropyl * * +22.0 (c 0.1,chloroform) 44 (Ex. 1)  cyclopropyl 81-85 +21.2 (c 0.1, chloroform) 77ethyl 64-65 R⁴ is Br Cmpd. No. R³ MP Optical Rotation 42 t-butyl 90-9173 cyclopropyl 71-75 R⁴ is I Cmpd. No. R³ MS MP Optical Rotation  87t-butyl 322.1 +19.2 (c 0.5, chloroform) 103 —CH₂C(Me)₃ 92-96 +111.2 (c0.25, chloroform) * See Index Table D for ¹H NMR data.

INDEX TABLE C-1

Comp. No. R^(1a) R^(1b) R³ MS/MP 46 2-methyl-3-furanyl cyclopropyl Hcyclopropyl 110-115 47 2-methyl-3-furanyl —CH₂CH₂— cyclopropyl * 483-methyl-2-thienyl Me H isopropyl 84-88 49 3-fluoro-2-thienyl Me Hcyclopropyl 72-76 50 3-bromo-2-thienyl Me H cyclopropyl 41-44 512-chloro-3-furanyl —CH₂CH₂— cyclopropyl 82-83 52 3-methyl-2-thienylcyclopropyl H cyclopropyl 121-125 53 2-chloro-3-furanyl ethyl Hcyclopropyl 74-77 54 2-chloro-3-furanyl ethyl H —CH₂OMe 54-55 555-iodo-2-methyl-4-thiazolyl methyl H cyclopropyl 337.3 565-iodo-4-thiazolyl methyl H cyclopropyl 323.3 572-chloro-4-iodo-5-thiazolyl methyl H cyclopropyl 357.2 583-methylthio-2-thienyl methyl H cyclopropyl 242.3 59 2-bromo-5-thiazoly1methyl H cyclopropyl 277.2 60 2-methyl-5-thiazolyl methyl H cyclopropyl211.3 61 5-thiazolyl methyl H cyclopropyl 197.3 62 5-chloro-4-thiazolylmethyl H cyclopropyl 231.3 63 5-bromo-4-thiazolyl methyl H cyclopropyl275.2 64 3-methoxy-2-thienyl methyl H cyclopropyl 60-62 653-(trifluoromethyl)-2-thienyl methyl H cyclopropyl 65-68 662-chloro-3-furanyl cyclopropyl H trifluoromethyl 101-106 672-methyl-3-furanyl ethyl H cyclopropyl 76-80 68 3-chloro-2-thienylcyclopropyl H cyclopropyl 160-164 69 2-thienyl methyl H cyclopropyl143-146 70 4-methyl-5-thiazolyl methyl H cyclopropyl 211.4 714-thiazolyl methyl H cyclopropyl 197.3 725-(trifluoromethyl)-4-thiazolyl methyl H cyclopropyl 265.3 824-methyl-5-thiazolyl methyl H t-butyl 114-118 893-(1,1-dimethylethyl)-2-thienyl methyl H isopropyl 67-68 903-(1,1-dimethylethyl)-2-thienyl methyl H t-butyl 68-69 935-bromo-4-thiazolyl methyl methyl —CH₂OMe 293.2 99 2-methyl-3-furanylt-butyl H t-butyl 285.1 * See Index Table D for ¹H NMR data.

INDEX TABLE C-2

R² is H Cmpd. No. O R^(1a) R^(1b) R³ MS/MP Optical Rotation 814-methyl-5-thiazolyl Me H t-butyl 125-129 +33.9 (c 0.1, chloroform)  913 -(1,1dimethylethyl)-2-thienyl H Me t-butyl 42-43 −33.1 (c 0.8,chloroform)  92 3-(1,1dimethylethyl)-2-thienyl Me H t-butyl 54-55 +17.3(c 0.79, chloroform) 95 3-cyano-2-thienyl Me H t-butyl 237.3 +26.4 (c0.78, chloroform) 100  4-methyl-3-thienyl Me H t-butyl 210.3 −35.1 (c0.77, chloroform)

INDEX TABLE D Cmpd. No. ¹H NMR Data ^(a)  5 ¹H NMR (CDCl₃) δ 7.26 (s,1H), 6.41 (s, 1H), 5.44 (br s, 1H), 4.15 (m, 1H), 2.58 (s, 3H), 1.50 (m,2H), 1.30 (m, 2H), 1.20 (d, 3H), 0.93 (t, 3H). 12 ¹H NMR (CDCl₃) δ 7.29(d, 1H), 6.78 (s, 1H), 6.50 (br s, 1H), 3.41 (s, 3H), 3.41 (s, 2H), 1.45(s, 6H). 17 ¹H NMR (CDCl₃) δ 7.31 (s, 1H), 6.82 (s, 1H), 6.00 (br s,1H), 4.18 (m, 1H), 1.5 (m, 2H), 1.30 (m, 2H), 1.22 (d, 1H), 0.95 (t,3H). 18 ¹H NMR (CDCl₃) δ 7.31 (s, 1H), 6.82 (s, 1H), 6.20 (br s, 1H),1.85 (s, 2H), 1.50 (s, 6H), 1.02 (s, 9H). 34 ¹H NMR (CDCl₃) δ 7.45 (s,1H), 6.80 (s, 1H), 6.05 (br s, 1H), 4.18 (m, 1H), 1.50 (m, 2H), 1.30 (m,2H), 1.23 (d, 3H), 0.95 (t, 3H). 35 ¹H NMR (CDCl₃) δ 7.46 (s, 1H), 6.87(s, 1H), 6.22 (br s, 1H), 4.07 (m, 1H), 1.17 (d, 3H), 0.97 (d, 6H). 43¹H NMR (CDCl₃) δ 7.32 (s, 1H), 6.84 (s, 1H), 6.25 (br s, 1H), 4.06 (m,1H), 1.79 (m, 1H), 1.17 (d, 3H), 0.96 (d, 6H). 47 ¹H NMR (CDCl₃) δ 7.08(s, 1H), 6.23 (s, 1H), 6.00 (br s, 1H), 2.42 (s, 3H), 1.35 (m, 1H), 0.60(m, 2H), 0.50 (m, 2H), 0.28 (m, 2H), 0.02 (m, 2H). 97 ¹H NMR (CDCl₃) δ7.46 (s, 1H), 6.47 (s, 1H), 5.24 (br s, 1H), 4.13 (m, 1H), 1.49-1.42 (m,2H), 1.24-1.19 (m, 3H), 0.95 (s, 9H). 98 ¹H NMR (CDCl₃) δ 7.42 (s, 1H),6.59 (br s, 1H), 4.24-4.20 (m, 1H), 1.63 (m, 1H), 1.55-1.44 (m, 1H),1.35-1.28 (m, 1H), 1.21 (d, 3H), 0.92-0.91 (m, 6H). ^(a 1)H NMR data arein ppm downfield from tetramethylsilane. Couplings are designated by(s)-singlet, (br s)-broad singlet, (d)-doublet, (t)-triplet,(m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets,(br)-broad.

A compound of this invention will generally be used as a parasiticnematode control active ingredient in a composition, i.e. formulation,with at least one additional component selected from the groupconsisting of surfactants, solid diluents and liquid diluents, whichserves as a carrier. The formulation or composition ingredients areselected to be consistent with the physical properties of the activeingredient, mode of application and environmental factors such as soiltype, moisture and temperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions and/or suspo-emulsions)and the like, which optionally can be thickened into gels. The generaltypes of aqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsionand suspo-emulsion. The general types of nonaqueous liquid compositionsare emulsifiable concentrate, microemulsifiable concentrate, dispersibleconcentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water. Spray volumes canrange from about one to several thousand liters per hectare, but moretypically are in the range from about ten to several hundred liters perhectare. Sprayable formulations can be tank mixed with water or anothersuitable medium for foliar treatment by aerial or ground application, orfor application to the growing medium of the plant. Liquid and dryformulations can be metered directly into drip irrigation systems ormetered into the furrow during planting. Liquid and solid formulationscan be applied onto seeds of crops and other desirable vegetation asseed treatments before planting to protect developing roots and othersubterranean plant parts and/or foliage through systemic uptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water- 0.001-90      0-99.999  0-15 soluble Granules, Tablets andPowders Oil Dispersions, Suspensions,  1-50 40-99  0-50 Emulsions,Solutions (including Emulsifiable Concentrates) Dusts  1-25 70-99 0-5Granules and Pellets 0.001-95      5-99.999  0-15 High StrengthCompositions 90-99  0-10 0-2

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol,triethylene glycol, propylene glycol, dipropylene glycol, polypropyleneglycol, propylene carbonate, butylene carbonate, paraffins (e.g., whitemineral oils, normal paraffins, isoparaffins), alkylbenzenes,alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, triacetin,aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes,alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone,isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamylacetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate,tridecyl acetate and isobornyl acetate, other esters such as alkylatedlactate esters, dibasic esters and γ-butyrolactone, and alcohols, whichcan be linear, branched, saturated or unsaturated, such as methanol,ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol,n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol,isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleylalcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol andbenzyl alcohol. Liquid diluents also include glycerol esters ofsaturated and unsaturated fatty acids (typically C₆-C₂₂), such as plantseed and fruit oils (e.g, oils of olive, castor, linseed, sesame, corn(maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean,rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beeftallow, pork tallow, lard, cod liver oil, fish oil), and mixturesthereof. Liquid diluents also include alkylated fatty acids (e.g.,methylated, ethylated, butylated) wherein the fatty acids may beobtained by hydrolysis of glycerol esters from plant and animal sources,and can be purified by distillation. Typical liquid diluents aredescribed in Marsden, Solvents Guide, 2nd Ed., Interscience, New York,1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquatemary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1, 1a, 1b or 2 and any other active ingredientsare typically incorporated into the present compositions by dissolvingthe active ingredient in a solvent or by grinding in a liquid or drydiluent. Solutions, including emulsifiable concentrates, can be preparedby simply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 μm can be wet milled using media mills toobtain particles with average diameters below 3 μm. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 μmrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. No.4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can beprepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, U K, 2000.

In the following Examples, all formulations are prepared in conventionalways. Compound numbers refer to compounds in Index Tables. Withoutfurther elaboration, it is believed that one skilled in the art usingthe preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Percentages are by weight except where otherwise indicated.

Example A

High Strength Concentrate

compound 9 98.5% silica aerogel  0.5% synthetic amorphous fine silica 1.0%

Example B

Wettable Powder

compound 11 65.0% dodecylphenol polyethylene glycol ether  2.0% sodiumligninsulfonate  4.0% sodium silicoaluminate  6.0% montmorillonite(calcined) 23.0%

Example C

Granule

compound 26 10.0% attapulgite granules (low volatile matter, 90.0%0.71/0.30 mm; U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet

compound 40 25.0% anhydrous sodium sulfate 10.0% crude calciumligninsulfonate  5.0% sodium alkylnaphthalenesulfonate  1.0%calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate

compound 43 10.0% polyoxyethylene sorbitol hexoleate 20.0% C₆-C₁₀ fattyacid methyl ester 70.0%

Example F

Microemulsion

compound 78  5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0%alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%

Example G

Seed Treatment

compound 80 20.00% polyvinylpyrrolidone-vinyl acetate copolymer  5.00%montan acid wax  5.00% calcium ligninsulfonate  1.00%polyoxyethylene/polyoxypropylene block copolymers  1.00% stearyl alcohol(POE 20)  2.00% polyorganosilane  0.20% colorant red dye  0.05% water65.75%

Example H

Fertilizer Stick

compound 84  2.5% pyrrolidone-styrene copolymer  4.8% tristyrylphenyl16-ethoxylate  2.3% talc  0.8% corn starch  5.0% slow-release fertilizer36.0% kaolin 38.0% water 10.6%

Example I

Suspension Concentrate

compound 9   35% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer  1.0% styrene acrylicpolymer  1.0% xanthan gum  0.1% propylene glycol  5.0% silicone baseddefoamer  0.1% 1,2-benzisothiazolin-3-one  0.1% water 53.7%

Example J

Emulsion in Water

compound 11 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer  1.0% styrene acrylicpolymer  1.0% xanthan gum  0.1% propylene glycol  5.0% silicone baseddefoamer  0.1% 1,2-benzisothiazolin-3-one  0.1% aromatic petroleum basedhydrocarbon 20.0 water 58.7%

Oil Dispersion

compound 26   25% polyoxyethylene sorbitol hexaoleate   15% organicallymodified bentonite clay  2.5% fatty acid methyl ester 57.5%

Example L

Suspoemulsion

compound 40 10.0% imidacloprid  5.0% butyl polyoxyethylene/polypropyleneblock copolymer  4.0% stearic acid/polyethylene glycol copolymer  1.0%styrene acrylic polymer  1.0% xanthan gum  0.1% propylene glycol  5.0%silicone based defoamer  0.1% 1,2-benzisothiazolin-3-one  0.1% aromaticpetroleum based hydrocarbon 20.0% water 53.7%

These present compounds and compositions are thus useful agronomicallyfor protecting field crops from parasitic nematodes, and alsononagronomically for protecting other horticultural crops and plantsfrom phytophagous parasitic nematodes. This utility includes protectingcrops and other plants (i.e. both agronomic and nonagronomic) thatcontain genetic material introduced by genetic engineering (i.e.transgenic) or modified by mutagenesis to provide advantageous traits.Examples of such traits include tolerance to herbicides, resistance tophytophagous pests (e.g., insects, mites, aphids, spiders, nematodes,snails, plant-pathogenic fungi, bacteria and viruses), improved plantgrowth, increased tolerance of adverse growing conditions such as highor low temperatures, low or high soil moisture, and high salinity,increased flowering or fruiting, greater harvest yields, more rapidmaturation, higher quality and/or nutritional value of the harvestedproduct, or improved storage or process properties of the harvestedproducts. Transgenic plants can be modified to express multiple traits.Examples of plants containing traits provided by genetic engineering ormutagenesis include varieties of corn, cotton, soybean and potatoexpressing an insecticidal Bacillus thuringiensis toxin such as YIELDGARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, INVICTARR2 PRO™, and herbicide-tolerant varieties of corn, cotton, soybean andrapeseed such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® andCLEARFIELD®, as well as crops expressing N-acetyltransferase (GAT) toprovide resistance to glyphosate herbicide, or crops containing the HRAgene providing resistance to herbicides inhibiting acetolactate synthase(ALS). The present compounds and compositions may interactsynergistically with traits introduced by genetic engineering ormodified by mutagenesis, thus enhancing phenotypic expression oreffectiveness of the traits or increasing the parasitic nematode controleffectiveness of the present compounds and compositions. In particular,the present compounds and compositions may interact synergistically withthe phenotypic expression of proteins or other natural products toxic toparasitic nematodes to provide greater-than-additive control of thesepests.

Compositions of this invention can also optionally comprise plantnutrients, e.g., a fertilizer composition comprising at least one plantnutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium,magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of noteare compositions comprising at least one fertilizer compositioncomprising at least one plant nutrient selected from nitrogen,phosphorus, potassium, sulfur, calcium and magnesium. Compositions ofthe present invention which further comprise at least one plant nutrientcan be in the form of liquids or solids. Of note are solid formulationsin the form of granules, small sticks or tablets. Solid formulationscomprising a fertilizer composition can be prepared by mixing thecompound or composition of the present invention with the fertilizercomposition together with formulating ingredients and then preparing theformulation by methods such as granulation or extrusion. Alternativelysolid formulations can be prepared by spraying a solution or suspensionof a compound or composition of the present invention in a volatilesolvent onto a previous prepared fertilizer composition in the form ofdimensionally stable mixtures, e.g., granules, small sticks or tablets,and then evaporating the solvent.

Compounds of this invention can exhibit activity against a wide spectrumof parasitic nematodes that live or grow inside or feed on plants (e.g.,foliage, fruit, stems, roots or seeds) or animals and humans (e.g.,vascular or digestive systems or other tissues) and therefore damagegrowing and stored agronomic crops, forestry, greenhouse crops,ornamentals and nursery crops, or afflict animal and human health. Cropsof particular interest are fruiting vegetables such as solanaceous andcucurbit crops, plantation crops such as banana and coffee, root cropssuch as potatoes, onion and carrots, and field crops such as tobacco,peanut, cotton, sugarcane and soybean.

Compounds of this invention can have activity on members of both classesAdenophorea and Secementea of the Phylum Nematoda, includingeconomically important members of the orders Enoplida, Dorylaimida,Rhabditida, Strongylida, Ascarida, Oxyurida, Spirurida, Tylenchida andAphelenchida, such as but not limited to economically importantagricultural pests such as root-knot nematodes of the genus Meloidogyne,cyst nematodes of the genera Heterodera and Globodera, lesion nematodesof the genus Pratylenchus, reniform nematodes of the genusRotylenchulus, burrowing nematodes of the genus Radopholus, stingnematodes of the genus Belonolaimus, spiral nematodes of the generaHelicotylenchus and Scutellonema, citrus nematodes of the genusTylenchulus, stubby root nematodes of the genera Trichodorus andParatrichodorus, dagger nematodes of the genus Xiphinema, stuntnematodes of the genus Tylenchorhynchus, needle nematodes of the generaLongidorus and Paralongidorus, lance nematodes of the genus Hoplolaimus,ring nematodes of the family Criconematidae, stem nematodes of thegenera Ditylenchus and Anguina, and foliar/stem nematodes of the generaAphelenchoides and Rhadinaphelenchus; and animal and human healthparasites (i.e. economically important roundworms such as Strongylusvulgaris in horses, Toxocara canis in dogs, Haemonchus contortus insheep, Dirofilaria immitis in dogs, etc.).

Of note is use of compounds of this invention for controlling southernroot-knot nematode (Meloidogyne incognita). Those skilled in the artwill appreciate that not all compounds are equally effective against allgrowth stages of all nematodes.

Compounds of this invention can also have activity on members of thePhylum Platyhelminthes, classes Cestoda (Tapeworms) and Trematoda(Flukes), including parasites (i.e. economically important flukes andtapeworms) afflicting animal and human health (e.g., Anoplocephalaperfoliata in horses, Fasciola hepatica in ruminants, etc.).

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including insecticides,fungicides, nematocides, bactericides, acaricides, herbicides, herbicidesafeners, growth regulators such as insect molting inhibitors androoting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, other biologically activecompounds or entomopathogenic bacteria, virus or fungi to form amulti-component pesticide giving an even broader spectrum of agronomicand nonagronomic utility. Thus the present invention also pertains to acomposition comprising a compound of Formula 1, 1a or 1b, and aneffective amount of at least one additional biologically active compoundor agent and can further comprise at least one of surfactants, soliddiluents or liquid diluents. For mixtures of the present invention, theother biologically active compounds or agents can be formulated togetherwith the present compounds, including the compounds of Formula 1, 1a or1b, to form a premix, or the other biologically active compounds oragents can be formulated separately from the present compounds,including the compounds of Formula 1, 1a or 1b, and the two formulationscombined together before application (e.g., in a spray tank) or,alternatively, applied in succession.

Examples of such biologically active compounds or agents with whichcompounds of this invention can be formulated are insecticides such asabamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate), amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin,bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl,carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr,chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clofentezin, clothianidin, cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyclaniliprole(3-bromo-N-[2-bromo-4-chloro-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide),cycloprothrin, cycloxaprid((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azepine),cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion,fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil,flometoquin(2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinylmethyl carbonate), flonicamid, flubendiamide, flucythrinate, flufenerim,flufenoxuron, flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate),fluensulfone(5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole),fluhexafon, fluopyram, flupiprole(1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile),flupyradifurone(4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone),fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate,halofenozide, heptafluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate),hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate),metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb,methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin,monocrotophos, monofluorothrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate),nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl,parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet,phosphamidon, pirimicarb, profenofos, profluthrin, propargite,protrifenbute, pyflubumide(1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide),pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriminostrobin (methyl(αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate),pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos,sulfoxaflor(N-[methyloxido[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-λ⁴-sulfanylidene]cyanamide),tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethrin, tetramethylfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2,3,3-tetramethylcyclopropanecarboxylate), tetraniliprole,thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen(3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin,triazamate, trichlorfon, triflumezopyrim(2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidiniuminner salt), triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.

Of note are insecticides such as abamectin, acetamiprid, acrinathrin,afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap,bifenthrin, buprofezin, cadusafos, carbaryl, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin,cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine,deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion,fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin,flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin, fluensulfone,flupiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate,heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb,lufenuron, meperfluthrin, metaflumizone, methiocarb, methomyl,methoprene, methoxyfenozide, metofluthrin, monofluorothrin, nitenpyram,nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin,pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin,thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin,triazamate, triflumezopyrim, triflumuron, Bacillus thuringiensisdelta-endotoxins, all strains of Bacillus thuringiensis and all strainsof nucleo polyhedrosis viruses.

One embodiment of biological agents for mixing with compounds of thisinvention include entomopathogenic bacteria such as Bacillusthuringiensis, and the encapsulated delta-endotoxins of Bacillusthuringiensis such as MVP® and MVPII® bioinsecticides prepared by theCellCap® process (CellCap®, MVP® and MVPII® are trademarks of MycogenCorporation, Indianapolis, Ind., USA); entomopathogenic fungi such asgreen muscardine fungus; and entomopathogenic (both naturally occurringand genetically modified) viruses including baculovirus, nucleopolyhedrovirus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV),Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus(GV) such as Cydiapomonella granulosis virus (CpGV).

Of particular note is such a combination where the other invertebratepest control active ingredient belongs to a different chemical class orhas a different site of action than the compound of Formula 1, 1a or 1b.In certain instances, a combination with at least one other invertebratepest control active ingredient having a similar spectrum of control buta different site of action will be particularly advantageous forresistance management. Thus, a composition of the present invention canfurther comprise at least one additional invertebrate pest controlactive ingredient having a similar spectrum of control but belonging toa different chemical class or having a different site of action. Theseadditional biologically active compounds or agents include, but are notlimited to, acetylcholinesterase (AChE) inhibitors such as thecarbamates methomyl, oxamyl, thiodicarb, triazamate, and theorganophosphates chlorpyrifos; GABA-gated chloride channel antagonistssuch as the cyclodienes dieldrin and endosulfan, and the phenylpyrazolesethiprole and fipronil; sodium channel modulators such as thepyrethroids bifenthrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, cypermethrin, deltamethrin, dimefluthrin,esfenvalerate, metofluthrin and profluthrin; nicotinicacetylcholinereceptor (nAChR) agonists such as the neonicotinoidsacetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram,nithiazine, thiacloprid, and thiamethoxam, and sulfoxaflor; nicotinicacetylcholine receptor (nAChR) allosteric activators such as thespinosyns spinetoram and spinosad; chloride channel activators such asthe avermectins abamectin and emamectin; juvenile hormone mimics such asdiofenolan, methoprene, fenoxycarb and pyriproxyfen; selectivehomopteran feeding blockers such as pymetrozine and flonicamid; mitegrowth inhibitors such as etoxazole; inhibitors of mitochondrial ATPsynthase such as propargite; ucouplers of oxidative phosphorylation viadisruption of the proton gradient such as chlorfenapyr; nicotinicacetylcholine receptor (nAChR) channel blockers such as the nereistoxinanalogs cartap; inhibitors of chitin biosynthesis such as thebenzoylureas flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron and triflumuron, and buprofezin; dipteran moultingdisrupters such as cyromazine; ecdysone receptor agonists such as thediacylhydrazines methoxyfenozide and tebufenozide; octopamine receptoragonists such as amitraz; mitochondrial complex III electron transportinhibitors such as hydramethylnon; mitochondrial complex I electrontransport inhibitors such as pyridaben; voltage-dependent sodium channelblockers such as indoxacarb; inhibitors of acetyl CoA carboxylase suchas the tetronic and tetramic acids spirodiclofen, spiromesifen andspirotetramat; mitochondrial complex II electron transport inhibitorssuch as the ß-ketonitriles cyenopyrafen and cyflumetofen; ryanidinereceptor modulators such as the anthranilic diamideschlorantraniliprole, cyantraniliprole and cyantraniliprole, diamidessuch as flubendiamide, and ryanodine receptor ligands such as ryanodine;compounds wherein the target site responsible for biological activity isunknown or uncharacterized such as azadirachtin, bifenazate, pyridalyl,pyrifluquinazon and triflumezopyrim; microbial disrupters of insectmidgut membranes such as Bacillus thuringensis and the delta-endotoxinsthey produce and Bacillus sphaericus; and biological agents includingnucleo polyhedro viruses (NPV) and other naturally occurring orgenetically modified insecticidal viruses.

Further examples of biologically active compounds or agents with whichcompounds of this invention can be formulated are: fungicides such asacibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine,azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil,benomyl, benthiavalicarb (including benthiavalicarb-isopropyl),benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen,blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate,carboxin, carpropamid, captafol, captan, carbendazim, chloroneb,chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride,copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil,cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine,dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol,dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M),dinocap, dithianon, dithiolanes, dodemorph, dodine, econazole,etaconazole, edifenphos, enoxastrobin (also known as enestroburin),epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone,fenamidone, fenaminstrobin, fenarimol, fenbuconazole, fenfuram,fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph,fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone,flometoquin, fluazinam, fludioxonil, flufenoxystrobin, flumorph,fluopicolide, fluopyram, fluoxastrobin, fluquinconazole, flusilazole,flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet,fthalide (also known as phthalide), fuberidazole, furalaxyl, furametpyr,hexaconazole, hymexazole, guazatine, imazalil, imibenconazole,iminoctadine albesilate, iminoctadine triacetate, iodicarb, ipconazole,isofetamid, iprobenfos, iprodione, iprovalicarb, isoprothiolane,isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb,mandipropamid, mandestrobin, maneb, mapanipyrin, mepronil,meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), metconazole,methasulfocarb, metiram, metominostrobin, metrafenone, myclobutanil,naftitine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone,ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid,oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron,penflufen, penthiopyrad, perfurazoate, phosphorous acid (including saltsthereof, e.g., fosetyl-aluminm), picarbutratox, picoxystrobin,piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, proquinazid, prothiocarb, prothioconazole,pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos,pyribencarb, pyributacarb, pyrifenox, pyriofenone, perisoxazole,pyrimethanil, pyrifenox, pyrrolnitrin, pyroquilon, quinconazole,quinmethionate, quinoxyfen, quintozene, silthiofam, sedaxane,simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole,tebufloquin, teclofthalam, tecloftalam, tecnazene, terbinafine,tetraconazole, thiabendazole, thifluzamide, thiophanate,thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolprocarb,tolyfluanid, triadimefon, triadimenol, triarimol, triazoxide, tribasiccopper sulfate, triclopyricarb, tridemorph, trifloxystrobin,triflumizole, trimoprhamide tricyclazole, triforine, triticonazole,uniconazole, validamycin, valifenalate (also known as valifenal),vinclozolin, zineb, ziram and zoxamide; nematocides such as fluopyram,spirotetramat, thiodicarb, fosthiazate, abamectin, iprodione,fluensulfone, dimethyl disulfide, tioxazafen, 1,3-dichloropropene(1,3-D), metam (sodium and potassium), dazomet, chloropicrin,fenamiphos, ethoprophos, cadusaphos, terbufos, imicyafos, oxamyl,carbofuran, tioxazafen, Bacillus firmus and Pasteuria nishizawae;bactericides such as streptomycin; acaricides such as amitraz,chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor,etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate,hexythiazox, propargite, pyridaben and tebufenpyrad.

In certain instances, combinations of a compound of this invention withother biologically active (particularly invertebrate pest control)compounds or agents (i.e. active ingredients) can result in agreater-than-additive (i.e. synergistic) effect. Reducing the quantityof active ingredients released in the environment while ensuringeffective pest control is always desirable. When synergism withinvertebrate pest control active ingredients occurs at application ratesgiving agronomically satisfactory levels of invertebrate pest control,such combinations can be advantageous for reducing crop production costand decreasing environmental load.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). Such anapplication may provide a broader spectrum of plant protection and beadvantageous for resistance management. The effect of the exogenouslyapplied compounds of this invention may be synergistic with theexpressed toxin proteins.

General references for these agricultural protectants (i.e.insecticides, fungicides, nematocides, acaricides, herbicides andbiological agents) include The Pesticide Manual, 13th Edition, C. D. S.Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U. K.,2003 and The BioPesticide Manual, 2^(nd) Edition, L. G. Copping, Ed.,British Crop Protection Council, Farnham, Surrey, U. K., 2001.

For embodiments where one or more of these various mixing partners areused, the weight ratio of these various mixing partners (in total) to acompound of Formula 1 is typically between about 1:3000 and about3000:1. Of note are weight ratios between about 1:300 and about 300:1(for example ratios between about 1:30 and about 30:1). One skilled inthe art can easily determine through simple experimentation thebiologically effective amounts of active ingredients necessary for thedesired spectrum of biological activity. It will be evident thatincluding these additional components can expand the spectrum ofparasitic nematodes controlled beyond the spectrum controlled by acompound of Formula 1 alone.

Parasitic nematodes are controlled in agronomic and nonagronomicapplications by applying one or more compounds of this invention,typically in the form of a composition, in a biologically effectiveamount, to the environment of the pests, including the agronomic and/ornonagronomic locus of infestation, to the area to be protected, ordirectly on the pests to be controlled.

Thus the present invention comprises a method for controlling aparasitic nematode in agronomic and/or nonagronomic applications,comprising contacting the parasitic nematode or its environment with abiologically effective amount of one or more of the compounds of theinvention, or with a composition comprising at least one such compoundor a composition comprising at least one such compound and at least oneadditional biologically active compound or agent. Examples of suitablecompositions comprising a compound of the invention and at least oneadditional biologically active compound or agent include granularcompositions wherein the additional active compound is present on thesame granule as the compound of the invention or on granules separatefrom those of the compound of the invention.

To achieve contact with a compound or composition of the invention toprotect a field crop from parasitic nematodes, the compound orcomposition is typically applied to the seed of the crop beforeplanting, to the foliage (e.g., leaves, stems, flowers, fruits) of cropplants, or to the soil or other growth medium before or after the cropis planted.

One embodiment of a method of contact is by spraying. Alternatively, agranular composition comprising a compound of the invention can beapplied to the plant foliage or the soil. Compounds of this inventioncan also be effectively delivered through plant uptake by contacting theplant with a composition comprising a compound of this invention appliedas a soil drench of a liquid formulation, a granular formulation to thesoil, a nursery box treatment or a dip of transplants. Of note is acomposition of the present invention in the form of a soil drench liquidformulation. Also of note is a method for controlling a parasiticnematode comprising contacting the parasitic nematode or its environmentwith a biologically effective amount of a compound of the presentinvention or with a composition comprising a biologically effectiveamount of a compound of the present invention. Of further note is thismethod wherein the environment is soil and the composition is applied tothe soil as a soil drench formulation. Of further note is that compoundsof this invention are also effective by localized application to thelocus of infestation. Other methods of contact include application of acompound or a composition of the invention by direct and residualsprays, aerial sprays, gels, seed coatings, microencapsulations,systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols,dusts and many others. One embodiment of a method of contact involves adimensionally stable fertilizer granule, stick or tablet comprising acompound or composition of the invention. The compounds of thisinvention can also be impregnated into materials for fabricatinginvertebrate control devices (e.g., insect netting).

Compounds of this invention are also useful in seed treatments forprotecting seeds from parasitic nematodes. In the context of the presentdisclosure and claims, treating a seed means contacting the seed with abiologically effective amount of a compound of this invention, which istypically formulated as a composition of the invention. This seedtreatment protects the seed from invertebrate soil pests and generallycan also protect roots and other plant parts in contact with the soil ofthe seedling developing from the germinating seed. The seed treatmentmay also provide protection of foliage by translocation of the compoundof this invention or a second active ingredient within the developingplant. Seed treatments can be applied to all types of seeds, includingthose from which plants genetically transformed to express specializedtraits will germinate. Representative examples of geneticallytransformed plants include those expressing proteins toxic to parasiticnematodes, such as Bacillus thuringiensis toxin or those expressingherbicide resistance such as glyphosate acetyltransferase, whichprovides resistance to glyphosate.

One method of seed treatment is by spraying or dusting the seed with acompound of the invention (i.e. as a formulated composition) beforesowing the seeds. Compositions formulated for seed treatment generallycomprise a film former or adhesive agent. Therefore typically a seedcoating composition of the present invention comprises a biologicallyeffective amount of a compound of Formula 1, 1a or 1b, and a film formeror adhesive agent. Seed can be coated by spraying a flowable suspensionconcentrate directly into a tumbling bed of seeds and then drying theseeds. Alternatively, other formulation types such as wetted powders,solutions, suspo-emulsions, emulsifiable concentrates and emulsions inwater can be sprayed on the seed. This process is particularly usefulfor applying film coatings on seeds. Various coating machines andprocesses are available to one skilled in the art. Suitable processesinclude those listed in P. Kosters et al., Seed Treatment: Progress andProspects, 1994 BCPC Mongraph No. 57, and references listed therein.

The treated seed typically comprises a compound of the present inventionin an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. fromabout 0.0001 to 1% by weight of the seed before treatment). A flowablesuspension formulated for seed treatment typically comprises from about0.5 to about 70% of the active ingredient, from about 0.5 to about 30%of a film-forming adhesive, from about 0.5 to about 20% of a dispersingagent, from 0 to about 5% of a thickener, from 0 to about 5% of apigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0to about 1% of a preservative, and from 0 to about 75% of a volatileliquid diluent.

For agronomic applications, the rate of application required foreffective control (i.e. “biologically effective amount”) will depend onsuch factors as the species of nematode to be controlled, the nematode'slife cycle, life stage, its size, location, time of year, host crop oranimal, feeding behavior, mating behavior, ambient moisture,temperature, and the like. Under normal circumstances, application ratesof about 0.01 to 2 kg of active ingredients per hectare are sufficientto control nematodes in agronomic ecosystems, but as little as 0.0001kg/hectare may be sufficient or as much as 8 kg/hectare may be required.For nonagronomic applications, effective use rates will range from about1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may besufficient or as much as 150 mg/square meter may be required. Oneskilled in the art can easily determine the biologically effectiveamount necessary for the desired level of parasitic nematode control.

The following Tests demonstrate the control efficacy of compounds ofthis invention on specific pests. “Control efficacy” representsinhibition of parasitic nematode development (including mortality) thatcauses significantly reduced feeding. The pest control protectionafforded by the compounds is not limited, however, to these species.

Biological Examples of the Invention Test A

Control of the southern root-knot nematode (Meloidogyne incognita)through contact and/or systemic means was evaluated in test unitsconsisting of small open containers filled with a sandy soil mixture andcucumber seedlings.

Test compounds were formulated using a solution containing 50% acetoneand 50% water. Test compounds were applied directly to the soil of thetest units at concentrations of 500 ppm active ingredient. Each test wasreplicated 3 times. After treatment, the test units were allowed to dryfor 1 hour, after which time about 400 second-stage juvenile (J2) larvaeand 800 eggs were pipetted into the soil. The test units were held at27° C. and watered as needed for 7 days.

Nematocidal efficacy was determined by the amount of root gall formationobserved when compared to an untreated control. No gall formation wasindicative of 100% nematode control. Gall formation equivalent to thatfound in the untreated control was indicative of 0% control. No nematodecontrol rating was given to compounds showing significant phytotoxicity.

Of the compounds tested at a concentration of 500 ppm, the followingprovided good levels of plant protection (50% or more reduction in rootgalling, compared to solvent-treated controls) and exhibited nosignificant phytotoxicity: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 14, 16,17, 18, 19, 20, 21, 22, 23, 24, 26, 27, 29, 30, 32, 33, 34, 35, 36, 37,39, 40, 42, 43, 45, 46, 47, 48, 50, 52, 53, 56, 58, 60, 62, 63, 65, 67,70, 72, 74, 75, 77, 80, 89, 90, 92, 95, 96, 101 and 103.

What is claimed is:
 1. A compound selected from Formula 1,

wherein R¹ is H or methyl; R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, each unsubstituted orsubstituted with at least one R⁵; R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl,C₂-C₁₆ alkynyl or C₃-C₆ cycloalkyl, each unsubstituted or substitutedwith at least one R⁶; R⁴ is Cl or Br; each R⁵ is independently halogen,cyano, C₁-C₃ alkoxy, C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃ alkylsulfonyl; each R⁶ is independently halogen,cyano, C₁-C₃ alkoxy, C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl or SiR^(a)R^(b)R^(c); and each R^(a),R^(b) and R^(c) is independently C₁-C₆ alkyl; provided that (i) when R¹and R² are H, then R³ is other than C₂-C₃ alkenyl, C₂-C₃ alkynyl,cyclopropyl, —CH₂OCH₃, —CH₂SCH₃, unsubstituted C₂-C₃ alkyl, or C₂-C₃alkyl substituted with Cl or Br (ii) when R¹ is methyl, then R³ is otherthan ethyl; and (iii) when R¹ is H and R² is methyl, then R³ is otherthan ethyl.
 2. A compound selected from Formula 1a,

wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkylthioor C₁-C₆ alkylsulfonyl, each unsubstituted or substituted with at leastone R⁵; R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆cycloalkyl, each unsubstituted or substituted with at least one R⁶; R⁴is Cl, Br, I, CH₃, CF₃ or cyano; each R⁵ is independently halogen,cyano, C₁-C₃ alkoxy, C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃ alkylsulfonyl; each R⁶ is independently halogen,cyano, C₁-C₃ alkoxy, C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl or SiR^(a)R^(b)R^(c); and each R^(a),R^(b) and R^(c) is independently C₁-C₆ alkyl.
 3. A compound selectedfrom Formula 1b,

wherein R² is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkylthioor C₁-C₆ alkylsulfonyl, each unsubstituted or substituted with at leastone R⁵; R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆cycloalkyl, each unsubstituted or substituted with at least one R⁶; R⁴is Cl, Br, I, CH₃, CF₃ or cyano; each R⁵ is independently halogen,cyano, C₁-C₃ alkoxy, C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃alkylsulfinyl or C₁-C₃ alkylsulfonyl; each R⁶ is independently halogen,cyano, C₁-C₃ alkoxy, C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃alkylsulfinyl, C₁-C₃ alkylsulfonyl or SiR^(a)R^(b)R^(c); and each R^(a),R^(b) and R^(c) is independently C₁-C₆ alkyl.
 4. The compound of any oneof claims 1, 2 and 3, wherein R² is H; R³ is —CR^(6a)R^(6b)R^(6c); R⁴ isCl or Br; R^(6a) is H, C₁-C₃ alkyl, C₂-C₃ alkenyl or C₃-C₆ cycloalkyl;R^(6b) is C₁-C₃ alkyl; R^(6c) is H, halogen, cyano, C₁-C₃ alkoxy, C₁-C₃alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ alkylsulfonyl or—CR^(7a)R^(7b)R^(7c); R^(7a) is H, halogen, cyano, C₁-C₃ alkoxy, C₁-C₃alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ alkylsulfonyl or C₁-C₂ alkyl;R^(7b) is H, halogen, cyano or C₁-C₂ alkyl; and R^(7c) is H, halogen,cyano or C₁-C₂ alkyl.
 5. A composition comprising (i) a compound ofFormula 1a and a compound of Formula 1b,

wherein the ratio of 1b to 1a is at least 55:45; and wherein R² is H; orC₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₂-C₆alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkylthio or C₁-C₆alkylsulfonyl, each unsubstituted or substituted with at least one R⁵;R³ is C₂-C₁₆ alkyl, C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆ cycloalkyl,each unsubstituted or substituted with at least one R⁶; R⁴ is Cl, Br, I,CH₃, CF₃ or cyano; each R⁵ is independently halogen, cyano, C₁-C₃alkoxy, C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl or C₁-C₃alkylsulfonyl; each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy,C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃alkylsulfonyl or SiR^(a)R^(b)R^(c); and each R^(a), R^(b) and R^(c) isindependently C₁-C₆ alkyl; and (ii) at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents.
 6. The composition of claim 5 wherein the ratio of 1bto 1a is at least 65:35.
 7. The composition of claim 5 wherein the ratioof 1b to 1a is at least 75:25.
 8. The composition of claim 5 wherein theratio of 1b to 1a is at least 85:15.
 9. The composition of claim 5wherein the ratio of 1b to 1a is at least 95:5.
 10. The composition ofclaim 5 wherein the ratio of 1b to 1a is at least 97:3.
 11. Thecomposition of claim 5 wherein the ratio of 1b to 1a is at least 99:1.12. The composition of claim 5 wherein the ratio of 1b to 1a isessentially 100:0.
 13. A composition comprising a compound of any one ofclaims 1 through 12, and at least one additional component selected fromthe group consisting of surfactants, solid diluents and liquid diluents,said composition optionally further comprising at least one additionalbiologically active compound or agent.
 14. The composition of any one ofclaims 5 through 12 wherein the compound of Formula 1b is present in anematocidally effective amount.
 15. The composition of claim 13 whereinthe at least one additional biologically active compound or agent isselected from the group consisting of abamectin, acephate, acequinocyl,acetamiprid, acrinathrin, afidopyropen, amidoflumet, amitraz,avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap,bifenthrin, bifenazate, bistrifluron, borate, buprofezin, cadusafos,carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr,chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clofentezin, clothianidin, cyantraniliprole, cyclaniliprole,cycloprothrin, cycloxaprid, cyflumetofen, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin,dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide,fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate,fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate,flufenerim, flufenoxuron, flufenoxystrobin, fluensulfone, fluopyram,flupyradifurone, fluvalinate, tau-fluvalinate, fonophos, formetanate,fosthiazate, halofenozide, heptafluthrin, hexaflumuron, hexythiazox,hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps,isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone,metaldehyde, methamidophos, methidathion, methiocarb, methomyl,methoprene, methoxychlor, methoxyfenozide, metofluthrin, monocrotophos,monofluorothrin, nicotine, nitenpyram, nithiazine, novaluron,noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate,phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin,propargite, protrifenbute, pyflubumide, pymetrozine, pyrafluprole,pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin,pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos,sulfoxaflor, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin,terbufos, tetrachlorvinphos, tetramethrin, tetramethylfluthrin,thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen,tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim,triflumuron, Bacillus thuringiensis delta-endotoxins, entomopathogenicbacteria, entomopathogenic viruses and entomopathogenic fungi.
 16. Thecomposition of claim 15 wherein the at least one additional biologicallyactive compound or agent is selected from the group consisting ofabamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin,azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, cadusafos,carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos,clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin,cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin,lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin,cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin,endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole,fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil,flometoquin, flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin,fluensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate,fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiocarb,methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin,nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine,pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen,ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen,spirotetramat, sulfoxaflor, tebufenozide, tetramethrin,tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim,triflumuron, Bacillus thuringiensis delta-endotoxins, all strains ofBacillus thuringiensis and all strains of nucleo polyhedrosis viruses.17. A method for controlling a soil-dwelling nematode comprisingcontacting the nematode or its environment with a biologically effectiveamount of a compound selected from Formula 2,

wherein Q is a furan, thiophene or thiazole ring substituted with R⁴ ata carbon atom adjacent to the carbon atom through which the furan,thiophene or thiazole ring is bonded to the remainder of Formula 2;R^(1a) is C₁-C₆ alkyl or C₃-C₆ cycloalkyl, each unsubstituted orsubstituted with at least one R⁵; R^(1b) is H or C₁-C₃ alkyl; or R^(1a)and R^(1b) are taken together with the carbon atom to which they areattached to form a 3- to 6-membered cycloalkyl ring, unsubstituted orsubstituted with at least one R⁵; R² is H; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₁-C₆ alkylthio or C₁-C₆ alkylsulfonyl, eachunsubstituted or substituted with at least one R⁵; R³ is C₂-C₁₆ alkyl,C₂-C₁₆ alkenyl, C₂-C₁₆ alkynyl or C₃-C₆ cycloalkyl, each unsubstitutedor substituted with at least one R⁶; R⁴ is Cl, Br, I, CH₃, CF₃ or cyano;provided that when R⁴ is Me, then R³ is other than unsubstituted C₂alkyl; each R⁵ is independently halogen, cyano, C₁-C₃ alkoxy, C₃-C₆cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, or C₁-C₃alkylsulfonyl; each R⁶ is independently halogen, cyano, C₁-C₃ alkoxy,C₃-C₆ cycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃alkylsulfonyl or SiR^(a)R^(b)R^(c); and each R^(a), R^(b) and R^(c) isindependently C₁-C₆ alkyl.
 18. The method of claim 17 wherein Q isselected from the group consisting of:


19. The method of claim 18 wherein Q is Q-1.
 20. The method of claim 17wherein the environment is a plant.
 21. The method of claim 17 whereinthe environment is a seed.
 22. The method of claim 21 wherein the seedis coated with the compound of Formula 2 formulated as a compositioncomprising a film former or adhesive agent.
 23. A method for controllinga soil-dwelling nematode comprising contacting the nematode or itsenvironment with a biologically effective amount of a composition of anyone of claims 5 through
 12. 24. A method for controlling a soil-dwellingnematode comprising contacting the nematode or its environment with abiologically effective amount of a compound of Formula 1b.
 25. Use of acomposition of any one of claims 5 through 12 as a nematocide.
 26. Atreated seed comprising a compound of any one of claims 1, 2, 3 or 4, inan amount of from about 0.0001 to 1% by weight of the seed beforetreatment.